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UNIVERSITI PUTRA MALAYSIA

MOHAMAD RASOOL MALEKBALA

FK 2012 89

PREPARATION, CHARACTERIZATION AND METHYLENE BLUE ADSORPTION OF SURFACTANT-TEMPLATED MESOPOROUS CARBON

COATED MONOLITH

i

PREPARATION, CHARACTERIZATION AND METHYLENE

BLUE ADSORPTION OF SURFACTANT-TEMPLATED

MESOPOROUS CARBON COATED MONOLITH


MASTER OF SCIENCE

UNIVERSITI PUTRA MALAYSIA

2012

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Abstract of thesis presented to the Senate of Universiti Putra Malaysia in

fulfillment of the requirement for the degree of Master of Science

PREPARATION, CHARACTERIZATION AND METHYLENE BLUE

ADSORPTION OF SURFACTANT-TEMPLATED MESOPOROUS CARBON

COATED MONOLITH

By


AUGUST 2012

Chairman : Professor Thomas Choong Shean Yaw, PhD

Faculty : Engineering

This thesis work brings the preparation and characterization of mesoporous carbon

coated monolith (MCCM) by using nonionic surfactant as template and its

application on adsorption of methylene blue. MCCM with high surface area and

pore volume was synthesized and characterized in detail. The preparation of

mesoporous carbon coated monoliths consisted of polymerization, dip-coating,

solidification and carbonization. MCCM have been prepared by dip-coating

cordierite monoliths in a polymer solution consists of furfuryl alcohol (carbon

source), F127 (template), pyrrole (binder) and nitric acid (polymerization catalyst).

After solidification of the polymer, the coating was carbonized at temperature of 700

oC to obtain MCCM. The influence of concentration of the surfactant template in

MCCM was investigated. It was found that by increasing the concentration of

surfactant, adsorption capacity of MCCM increases from 100 to 200 mg/g. The

mesoporous carbon coated monoliths are characterized by nitrogen adsorption-

desorption, thermogeravimetric analysis, scanning electron microscopy and Fourier

transform infrared. The characterization study shows that the MCCM prepared in

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this work possesses a higher surface area (842 m2/g), pore volume (0.3 m

3/g) and

mesoporosity (97%) compare to previous study (MCCM by PEG). The potential of

mesoporous carbon coated monolith on the adsorption of methylene blue dye was

investigated. Batch adsorption experiments were carried out to find out the effects of

pH (2-11), salt, contact times (4480 min), initial dye concentrations (50-400 ppm)

and temperature (25, 35 and 45 oC) on the adsorption of the dye. pH was found to be

the most significant factor and pH 10 was favorable for MB adsorption.

Furthermore, kinetic study showed that the adsorption could be better represented by

the pseudo-second-order model. Equilibrium adsorption data were predicted by two

isotherms, i.e. the Langmuir and the Freundlich isotherms. The best fit to the data

was obtained with the Langmuir isotherm with maximum monolayer adsorption

capacity of 388 mg/g. Adsorption of MB is favourably influenced by an increase in

the temperature of the operation from 388 to 440 mg/g. By associated

thermodynamic parameters, the adsorption was found to be spontaneous and

endothermic. Desorption study indicates that 0.1N hydrochloric acid exhibits higher

elution efficiency and a quantitative recovery of MB (around 82%) can be achieved.

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Abstrak tesis ini dikemukakan kepada Senat Universiti Putra Malaysia bagi

memenuhi keperluan untuk ijazah Master Sains

PENYEDIAAN, PENCIRIAN, DAN PENJERAPAN METILENA BIRU KE

ATAS MESOPOROUS MONOLIT BERSALUT KARBON DENGAN

MENGGUNAKAN SURFAKTAN SEBAGAI TEMPLATE

Oleh


OGOS 2012

Pengerusi : Profesor Thomas Choong Shean Yaw, PhD

Fakulti : Kejuruteraan

Tesis ini merangkumi penyediaan dan pencirian karbon mesoporous bersalut

monolit (MCCM) dengan menggunakan surfaktan tidak berion sebagai acuan dan

aplikasinya dalam penjerapan metil etena biru. MCCM yang mempunyai luas

permukaan dan isipadu liang yang tinggi dihasilkan dan dicirikan dengan teliti.

Penyediaan mesoporous monolit bersalut karbon adalah melalui kaedah

pempolimeran, celup dan salut, pemejalan dan karbonisasi. MCCM disediakan

dengan mencelupdan salut kordierit monolit ke dalam larutan polimer yang

mengandungi alkohol furfuryl (sumber karbon), F127 (bahan acuan), pirola (ikatan)

dan asid nitrik (pemangkin pempolimeran). Setelah pemejalan polimer dilakukan,

salutan tadi dikarbonkan pada suhu 700 oC untuk menghasilkan MCCM. Kajian

mengenai pengaruh kepekatan surfaktan di atas acuan di dalam MCCM telah dikaji.

Hasil analisis menunjukkan bahawa dengan meningkatkan kuantiti surfaktan,

keupayaan penjerapan MCCM turut meningkat dari 100 ke 200 mg/g. Mesoporous

monolit bersalut karbon telah dicirikan melalui proses penjerapan dan penyahjerapan

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nitrogen, analisis geravimetrik termo, analisis pengimbasan mikroskop elektron dan

juga melalui kaedah Fourier inframerah. Hasil kajian menunjukkan bahawa

penyediaan MCCM melalui kaedah ini telah berupaya untuk menghasilkan luas

permukaan dan liang isipadu yang tinggi berbanding dengan kajian terdahulu

(MCCM menggunakan PEG). Potensi mesoporous karbon yang bersalut monolit

terhadap penjerapan pewarna metil etena biru telah dikaji. Eksperimen penjerapan

secara berkumpulan telah dijalankan untuk melihat kesan terhadap pH (2-11),

garam, masa sentuh (4480 min), kepekatan asal pewarna (50-400 ppm) dan suhu

(25, 35 and 45 oC) ke atas penjerapan warna. Kesan pH didapati menunjukkan

keputusan amat signifikasi dan pH 10 adalah terbaik untuk penjerapan MB.

Tambahan pula, kajian kinetik menunjukkan bahawa penjerapan adalah lebih baik

dengan menggunakan model pseudo-tertib-kedua. Keseimbangan penjerapan data

telah diramal dengan menggunakan dua isoterma iaitu Langmuir dan Freundlich.

Padanan terbaik data telah diperolehi melalui isoterma Langmuir dengan keupayaan

penjerapan maksimum sebanyak 388 mg/g. Penjerapan MB banyak dipengaruhi oleh

peningkatan suhu kajian dari 388 ke 400 mg/g. Penjerapan dilihat sebagai spontan

dan endotermik berpandukan kepada termodinamik parameter . Penyahjerapan

menunjukkan bahawa penggunaan 0.1N asid hidroklorik boleh mempamerkan

kecekapan elusi yang lebih tinggi dan pemulihan kuantitatif MB (anggaran 82%)

dapat dicapai.

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ACKNOWLEDGEMENTS

In the name of Allah the Most Merciful and Most Beneficent, to whom I express all

the thankfulness and gratitude as if not of HIM I would not able to finish this work.

Without HIM I lacked the knowledge, strength and patience to overcome the tough

and unpredicted obstacles I had faced along this journey. I shall be thankful to HIM

all my life, Insya-Allah.

I wish to express my sincere gratitude and appreciation to my supervisor Associate

Professor Thomas Choong Shean Yaw for his comments and personal guidance

throughout my study. I also wish to thank my co-supervisors Professor Luqman

Chuh Abdullah and Dr. Soraya Hosseini for their valuable input to this work.

I am very much gratified to all the academic staff, technicians and administrative

staff of the Department of Chemical and Environmental Engineering. My thanks are

also extended to all my friends and colleagues who gave me all kind of support

during my study.

I would like to express my most sincere and warmest gratitude to my parents,

brothers, and sisters for their prayer, loving, and moral inputs especially during the

most difficult times I faced along this period.

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I certify that an Examination Committee has met on 28th of August 2012 to

conductthe final examination of name of Mohamad Rasool Malekbala on his Master

of Science thesis entitled “Preparation, Characterization and Methylene Blue

Adsorption of Surfactant-Templated Mesoporous Carbon Coated Monolith" in

accordance with Universiti Pertanian Malaysia (Higher Degree) Act 1980 and

Universiti Pertanian Malaysia (Higher Degree) Regulations 1981. The Committee

recommends that the candidate be awarded the relevant degree. Members of the

Examination Committee are as follows:

Tinia Idaty Mohd. Ghazi, PhD

Lecturer

Faculty of Engineering

Universiti Putra Malaysia

(Chairman)

Dayang Radiah Awang Biak, PhD

Lecturer



(Internal Examiner)

Taufiq Yap Yun Hin, PhD

Professor



(Internal Examiner)

Bassim H. Hameed, PhD

Professor


Universiti Sains Malaysia

(External Examiner)

BUJANG KIM HUAT, PhD

Professor/Deputy Dean

School of Graduate Studies


Date:

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This thesis was submitted to the Senate of Universiti Putra Malaysia and has been

accepted as fulfillment of the requirement for the degree of Master of Science. The

members of the Supervisory Committee were as follows:

Thomas Choong Shean Yaw, PhD

Professor



(Chairman)

Luqman Chuah Abdullah, PhD

Professor



(Member)

BUJANG BIN KIM HUAT, PhD

Professor and Dean

School of Graduate Studies


Date: 13 December 2012

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DECLARATION

I declare that the thesis is my original work except for quotations and citations

which have been duly acknowledged. I also declare that it has not been previously

and it is not concurrently, submitted for any other degree at Universiti Putra

Malaysia or other institutions.


Date: 28 August 2012

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TABLE OF CONTENTS

Page

ABSTRACT ii

ABSTRAK iv

ACKNOWLEDGEMENT vi

APPROVAL vii

DECLARATION ix

LIST OF TABLES xii

LIST OF FIGURES xiv

LIST OF NOMENCLATURE xvi

CHAPTER

1 INTRODUCTION

1.1 Background

1

1.2 Problem Statement

4

1.3 Objectives of the Study 5

1.4 Scope of Work

6

1.5 Outline of Thesis

7

2 LITRATURE REVIEW

2.1 Introduction

8

2.2 Porous Materials

9

2.2.1 Porous Carbon 10

2.3 Surfactant (Template) 10

2.3.1 Micellization of Surfactant 12

2.3.2 Surfactant in Porous Carbon 13

2.4 Honeycomb Monolith 15

2.4.1 Carbon Coated Monolith 18

2.5 Adsorbent Characterization 18

2.5.1 Physical Characterization 18

2.5.1.1 Nitrogen Adsorption/Desorption 19

2.6 Adsorption of Dye

25

2.6.1 Adsorption Concept 26

2.6.2 Adsorption of Methylene Blue 26

2.6.3 Adsorption Isotherms 27

2.6.3.1 Langmuir Isotherm 28

2.6.3.2 Freundlich Isotherm 28

2.6.4 Kinetic Studies 29

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2.6.4.1 Pseudo First Order Kinetic Model 30

2.6.4.2 Pseudo Second Order Kinetic Model 30

2.6.4.3 Intra-Particle Diffusion 31

2.6.5 Thermodynamics Model 32

2.7 Summary

34

3 MATERIALS AND METHODS

3.1 Materials and Chemicals 36

3.2 Equipment

38

3.3 Production of MCCM 38

3.3.1 Effect of F127 on the Preparation of the MCCM 39

3.4 Characterization of MCCM 41

3.4.1 Amount of Coating 41

3.4.2 Physical Characterization 42

3.4.2.1 Nitrogen Adsorption/Desorption 42

3.4.2.2 Scanning Electron Microscopy 43

3.4.2.3 Fourier Transform-Infrared Spectroscopy 43

3.4.2.4 Thermogravimetric Analysis 43

3.4.3 Chemical Characterization 44

3.4.3.1 Boehm Titration 44

3.4.3.2 Determination of Point Zero Charge 44

3.5 Batch Experimental Studies 45

3.5.1 Preparation of Calibration Curve 45

3.5.2 Effect of pH

46

3.5.3 Effect of Ionic Strength 46

3.5.4 Effect of Contact Time and Dye Concentrations 47

3.5.5 Effect of Temperature 47

3.5.6 Desorption Experiment 47

4 RESULTS AND DISCUSSION

4.1 Introduction

49

4.2 Effect of F127 on the Preparation of the MCCM 50

4.3 Amount of Mass Change during Coating and Carbonization 52

4.4 Characterization of MCCM 53

4.4.1 Nitrogen Adsorption-Desorption 53

4.4.2 Scanning Electron Microscope 57

4.4.3 Thermogravimetric Analysis 59

4.4.4 Fourier Transform Infrared Spectroscopy 60

4.5 Chemical Characterizations 61

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4.5.1 Boehm Titration 61

4.2.2 pHPZC

61

4.6 Methylene Blue Adsorption 62

4.6.1 Fourier Transform Infrared Spectroscopy 62

4.6.2 Effect of pH

63

4.6.3 Effect of Ionic Strength 65

4.6.4 The Effect of Contact Time and Dye Concentration 66

4.6.5 Kinetics Study 68

4.6.6 Adsorption Isotherm 71

4.6.6.1 Freundlich Isotherm 71

4.6.6.2 Langmuir Isotherm 72

4.6.7 Effect of Temperature 75

4.6.8 Thermodynamic Parameters 76

4.7 Adsorption-Desorption and Re-adsorption of MB on MCCM 78

4.7.1 Effect of Elution Agents on MB Desorption 78

4.7.2 Effect of HCl Concentration on MB Desorption 79

4.7.3 Successive Cycles of MB Adsorption and Desorption 79

4.8 Comparison with Previous Work 81

4.9 Summary 81

5 CONCLUSIONS AND SUGGESTIONS

5.1 Conclusions

83

5.2 Recommendations for Future Work 84

REFERENCES 85

APPENDICES 96

BIODATA OF STUDENT 106

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PREPARATION, CHARACTERIZATION AND METHYLENE BLUE ADSORPTION OF SURFACTANT-TEMPLATED MESOPOROUS CARBON COATED MONOLITHAbstractTABLE OF CONTENTSCHAPTERREFERENCES

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